JP2002306936A - High heat-resistant porous tubular membrane and method for manufacturing the same - Google Patents
High heat-resistant porous tubular membrane and method for manufacturing the sameInfo
- Publication number
- JP2002306936A JP2002306936A JP2001118314A JP2001118314A JP2002306936A JP 2002306936 A JP2002306936 A JP 2002306936A JP 2001118314 A JP2001118314 A JP 2001118314A JP 2001118314 A JP2001118314 A JP 2001118314A JP 2002306936 A JP2002306936 A JP 2002306936A
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- Japan
- Prior art keywords
- heat
- resistant
- tubular membrane
- fiber bundle
- resistant porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、優れた耐熱性、耐
腐食性、耐圧性能、及び形態安定性を有し、かつ高強度
で濾過効率の高い高耐熱性多孔質管状膜およびその製造
方法に関し、本発明によって得られる高耐熱性多孔質管
状膜は原子力発電および火力発電における復水の濾過な
ど、主に高温、高圧下での気液混合相や液相における分
離膜として有用に用いられる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly heat-resistant porous tubular membrane having excellent heat resistance, corrosion resistance, pressure resistance and form stability, high strength and high filtration efficiency, and a method for producing the same. The high heat-resistant porous tubular membrane obtained by the present invention is useful as a separation membrane in a gas-liquid mixed phase or a liquid phase mainly at high temperature and high pressure, such as filtration of condensate in nuclear power generation and thermal power generation. .
【０００２】[0002]
【従来の技術】近年の化学工業をはじめ各分野での技術
の進歩は著しく、濾過材に対しては、高温、高圧に耐
え、更に一層の耐食性向上が要求されている。2. Description of the Related Art In recent years, technological progress in various fields including the chemical industry has been remarkable, and filter materials are required to withstand high temperatures and high pressures and to further improve corrosion resistance.
【０００３】従来、高温高圧下での気液混合相や液相に
おける濾過材としては、高温下での比強度が高い金属焼
結フィルター又はセラミックフィルター、炭素繊維をベ
ースとした濾過材料などが一般的に用いられてきた。Conventionally, as a filtering material in a gas-liquid mixed phase or a liquid phase under a high temperature and a high pressure, a metal sintered filter or a ceramic filter having a high specific strength at a high temperature and a filtering material based on carbon fiber are generally used. It has been used regularly.
【０００４】しかしながら、金属焼結フィルターの場
合、構成金属が溶出する恐れがあり、耐酸性が不十分の
場合がある。また、セラミックフィルターの場合、耐酸
性は十分であるが、粒子が溶出する恐れがあり、特にＳ
ｉは堆積して、フィルター及び配管等を閉塞する場合が
ある。[0004] However, in the case of a metal sintered filter, constituent metals may be eluted, and the acid resistance may be insufficient. Further, in the case of a ceramic filter, although the acid resistance is sufficient, particles may be eluted.
i may accumulate and block filters and piping.
【０００５】また、両者とも工業用装置としては、中空
状フィルターと比較して一般的に濾過効率が低い。[0005] In both cases, the filtration efficiency is generally lower than that of a hollow filter as an industrial device.
【０００６】一方、炭素繊維を基材とする多孔質フィル
ターは、高温に耐え、更に耐食性も良好である等のすぐ
れた特徴を有しており、以下の公報に見られる報告がな
されている。On the other hand, a porous filter using carbon fiber as a base material has excellent characteristics such as withstanding high temperatures and good corrosion resistance, and has been reported in the following gazettes.
【０００７】特開昭５７−１６６３５４号公報には、炭
素繊維を基材とする紙状多孔質体が記載されているが、
濾紙の代替材料として用いられるものであって固体と液
体を分離する程度の平膜である。さらに平膜として供さ
れるため単位体積当たりの膜面積は小さく、モジュール
として用いる場合は不利であると考えられる。Japanese Patent Application Laid-Open No. 57-166354 describes a paper-like porous material having carbon fiber as a base material.
A flat membrane that is used as an alternative to filter paper and separates solids and liquids. Furthermore, since it is provided as a flat membrane, the membrane area per unit volume is small, and it is considered disadvantageous when used as a module.
【０００８】また、特公昭５１−５０９０号公報にはフ
ェノール樹脂を出発原料とした中空状炭素系材料が記載
されているが、この中空状炭素系材料はフェノール樹脂
を溶融紡糸して得た中実繊維を架橋剤で一部架橋し、次
いで未架橋部分を溶媒で溶出することによって中空繊維
とし、これを炭化することによって製造される。この様
な製造方法によれば、炭素体中に強制的にボイドが形成
されるため、表面付近にも比較的大きなボイドが存在す
る恐れがあり、強度、耐圧性能および形態安定性が不足
する恐れがある。Japanese Patent Publication No. 51-5090 discloses a hollow carbon-based material using a phenolic resin as a starting material. This hollow carbon-based material is obtained by melt-spinning a phenolic resin. It is produced by partially crosslinking a real fiber with a crosslinking agent and then eluting an uncrosslinked portion with a solvent to form a hollow fiber, which is carbonized. According to such a manufacturing method, since voids are forcibly formed in the carbon body, relatively large voids may be present near the surface, and strength, pressure resistance and morphological stability may be insufficient. There is.
【０００９】更に、特開昭６０−２０２７０３号公報に
は、外径１０μｍ〜１０ｍｍの中空状炭素膜が記載され
ているが、当該公報においては、太径の単糸に強制的に
ボイドを生成させるため、炭素繊維が本来有する高い強
度が損なわれる恐れがある。また、太径の原糸を用いる
ため耐炎化および炭化に要する時間は、一般の炭素繊維
のそれと比較して長くなる傾向にあり、生産性が不十分
となる恐れがある。加えて、所望の膜厚、孔径、孔の配
列などを実現するためには製造条件を厳しく管理する必
要があると考えられ、十分な生産性が実現できない恐れ
がある。Furthermore, Japanese Patent Application Laid-Open No. Sho 60-202703 describes a hollow carbon membrane having an outer diameter of 10 μm to 10 mm. In this publication, voids are forcibly formed in a large-diameter single yarn. Therefore, the high strength inherent in the carbon fiber may be impaired. In addition, since a large-diameter raw yarn is used, the time required for flame resistance and carbonization tends to be longer than that of general carbon fibers, and the productivity may be insufficient. In addition, in order to achieve a desired film thickness, hole diameter, arrangement of holes, and the like, it is considered necessary to strictly control manufacturing conditions, and sufficient productivity may not be realized.
【００１０】以上の様に、従来の分離膜には、高温およ
び高圧下での使用を目的とした更なる性能の向上が求め
られているのが現状である。As described above, at present, the conventional separation membrane is required to further improve its performance for use under high temperature and high pressure.
【００１１】[0011]
【発明が解決しようとする課題】上記の状況に鑑み、本
発明においては、高温および高圧下での気液混合相また
は液相における分離膜としては好適に使用することがで
きる高い耐熱性を有し、耐食性に優れ、高圧下でも管状
構造の形態安定性に優れ、取扱い性に優れ、耐久性があ
り、濾過性能が良好かつ濾過効率に優れた高耐熱性多孔
質管状膜を提供することを目的とする。In view of the above situation, the present invention has a high heat resistance which can be suitably used as a separation membrane in a gas-liquid mixed phase or a liquid phase under high temperature and high pressure. To provide a highly heat-resistant porous tubular membrane having excellent corrosion resistance, excellent morphological stability of the tubular structure even under high pressure, excellent handleability, durability, good filtration performance and excellent filtration efficiency. Aim.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するため
の本発明によれば、主に耐熱性繊維束の構造形成体から
なる管状支持体と、該管状支持体の内面および外面の少
なくとも一方に形成され、粒子状物質の分離機能を有す
る耐熱性多孔質層とを含んでなることを特徴とする高耐
熱性多孔質管状膜が提供される。According to the present invention for achieving the above object, according to the present invention, a tubular support mainly comprising a structure forming body of a heat-resistant fiber bundle, and at least one of an inner surface and an outer surface of the tubular support And a heat-resistant porous layer having a function of separating particulate matter.
【００１３】また、主に耐熱性繊維束を構造形成して管
状支持体を製造する工程と、該管状支持体の内面および
外面の少なくとも一方に、多孔質層の原料体をコーティ
ングする工程と、コーティングされた管状支持体を、所
定の温度で熱処理することにより多孔質層を形成する工
程とを含んでなる方法により、本発明の高耐熱性多孔質
管状膜を製造することができる。A step of mainly forming a heat-resistant fiber bundle to form a tubular support, and a step of coating at least one of an inner surface and an outer surface of the tubular support with a raw material of a porous layer; Subjecting the coated tubular support to heat treatment at a predetermined temperature to form a porous layer, whereby the highly heat-resistant porous tubular membrane of the present invention can be produced.
【００１４】本発明の高耐熱性多孔質管状膜において
は、例えば、組み紐などの繊維束からなる管状支持体に
ポリスルホン及びＰＶＤＦ等の多孔質体を担持させた膜
や、多孔質体を炭化させた膜等の従来例と異なり、支持
体および多孔質層の何れにおいても耐熱性の素材が使用
される。このため、良好な膜透過性能を維持しながら、
強度および耐熱性を向上することができる。In the highly heat-resistant porous tubular membrane of the present invention, for example, a membrane in which a porous body such as polysulfone or PVDF is supported on a tubular support made of a fiber bundle such as a braid, or the porous body is carbonized. Unlike the conventional example such as a membrane, a heat-resistant material is used for both the support and the porous layer. For this reason, while maintaining good membrane permeation performance,
Strength and heat resistance can be improved.
【００１５】結果として、高温および高圧下での気液混
合相または液相における分離膜として好適に使用できる
高耐熱性多孔質管状膜に関し、高い耐熱性および耐食
性、高圧下での管状構造の形態安定性、良好な耐久性お
よび取扱い性、十分な濾過性能および濾過効率を実現す
ることができる。As a result, the present invention relates to a high heat-resistant porous tubular membrane which can be suitably used as a separation membrane in a gas-liquid mixed phase or a liquid phase under high temperature and high pressure, and has a high heat resistance and corrosion resistance, and a tubular structure under high pressure. Stability, good durability and handleability, sufficient filtration performance and filtration efficiency can be realized.
【００１６】また、本発明の高耐熱性多孔質膜は管状で
あるため、平膜と比較して、モジュールとして用いた場
合に単位体積当たりの膜面積が大きくできるという点で
特に有効である。Further, since the high heat-resistant porous membrane of the present invention is tubular, it is particularly effective in that the membrane area per unit volume can be increased when used as a module as compared with a flat membrane.
【００１７】[0017]
【発明の実施の形態】本発明の具体的な実施の形態例に
ついて、図面を用いて詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described in detail with reference to the drawings.
【００１８】図１は、高耐熱性多孔質管状膜の一例とし
て、管状支持体１０と多孔質層２０及び多孔質層３０と
からなる場合を示した。FIG. 1 shows a case where a tubular support 10 and a porous layer 20 and a porous layer 30 are formed as an example of a highly heat-resistant porous tubular membrane.
【００１９】被処理流体は、まず管状支持体１０の内面
もしくは外面に供給され、管状支持体１０と多孔質層２
０及び３０との略同心円の半径方向へ移動する際に濾過
作用を受けるものであり、濾過作用を受ける際の移動方
向は内面から外面、外面から内面の何れでも良い。The fluid to be treated is first supplied to the inner or outer surface of the tubular support 10, and the tubular support 10 and the porous layer 2 are supplied.
It is subjected to a filtering action when moving in a radial direction of a substantially concentric circle with 0 and 30, and the moving direction when receiving the filtering action may be any of the inner surface to the outer surface and the outer surface to the inner surface.
【００２０】図１の場合、多孔質層は管状支持体１０の
内面および外面の両表面上に形成されているが、多孔質
層２０のみ（内面のみに）形成されても良く、多孔質層
３０のみ（外面のみに）形成されても良く、流体性状を
考慮したうえで目的に応じて適宜選択される。In FIG. 1, the porous layer is formed on both the inner surface and the outer surface of the tubular support 10, but may be formed only on the porous layer 20 (only on the inner surface). Only 30 (only on the outer surface) may be formed, and it is appropriately selected according to the purpose in consideration of fluid properties.
【００２１】また、多孔質層３０の外周面上に更に多孔
質層を形成しても良く、同様に多孔質層２０の内周面上
に更に多孔質層を形成しても良く、多孔質層の層の数お
よび管状支持体に対する多孔質層の形成方向は、特に制
限されない。Further, a porous layer may be further formed on the outer peripheral surface of the porous layer 30, and a porous layer may be further formed on the inner peripheral surface of the porous layer 20. The number of layers and the direction in which the porous layer is formed with respect to the tubular support are not particularly limited.
【００２２】最外層または最内層における多孔質層の最
大孔径は、所望する分離能および膜特性に応じて適宜決
定される。一般的な精密ろ過における粒子状物質の良好
な分離機能を実現するためには、最大孔径は３μｍ以下
とすることが好ましく、１μｍ以下がより好ましい。The maximum pore size of the porous layer in the outermost layer or the innermost layer is appropriately determined according to the desired separation ability and membrane characteristics. In order to realize a good function of separating particulate matter in general microfiltration, the maximum pore size is preferably 3 μm or less, more preferably 1 μm or less.
【００２３】一般的に膜構造を有する多孔質層を得るた
めの原料体としては、例えば、セルロース、ピッチ、ポ
リアミド、ポリエステル、ポリスルホン、ポリビニルア
ルコール、ポリアクリロニトリル、ポリスチレン、ポリ
オレフィン等が挙げられるが、本発明の趣旨である高耐
熱膜の観点からは熱処理後の耐熱性、膜強度および形態
安定性等に優れるポリアクリロニトリル系重合体または
フェノール樹脂に代表される熱硬化性樹脂であることが
好ましい。In general, examples of a raw material for obtaining a porous layer having a membrane structure include cellulose, pitch, polyamide, polyester, polysulfone, polyvinyl alcohol, polyacrylonitrile, polystyrene, polyolefin and the like. From the viewpoint of a high heat-resistant film, which is the gist of the present invention, a thermosetting resin represented by a polyacrylonitrile-based polymer or a phenol resin, which is excellent in heat resistance after heat treatment, film strength, shape stability, and the like, is preferable.
【００２４】なお、ポリアクリロニトリル系重合体とし
ては例えば重量平均分子量が１００００以上のものが使
用され、ポリアクリロニトリル系重合体の粉体を含有ま
たは溶解するポリマー液を用いることができ、溶媒、液
中のポリマー濃度、液粘度等の条件は特に制限されな
い。As the polyacrylonitrile polymer, for example, those having a weight average molecular weight of 10,000 or more can be used, and a polymer solution containing or dissolving a powder of the polyacrylonitrile polymer can be used. The conditions such as the polymer concentration and the liquid viscosity are not particularly limited.
【００２５】またフェノール樹脂としては、通常市販さ
れるフェノール樹脂を用いることができ、樹脂製法、溶
媒、溶液粘度等の条件は特に制限されない。As the phenol resin, a commercially available phenol resin can be used, and conditions such as a resin production method, a solvent, and a solution viscosity are not particularly limited.
【００２６】これらの原料体は、そのままの状態で、ま
た、上述の如く適当な溶媒に溶解または分散され、ディ
ップ及びコーティング等の方法により管状支持体の表面
に塗布される。その後、所望の最大孔径、耐熱性、膜強
度および形態安定性等を実現するために、所定の加熱温
度および時間により熱処理され多孔質層とされる。These raw materials are dissolved or dispersed in an appropriate solvent as described above and applied to the surface of the tubular support by a method such as dip and coating. Thereafter, in order to realize desired maximum pore diameter, heat resistance, membrane strength, morphological stability, and the like, the porous layer is heat-treated at a predetermined heating temperature and time.
【００２７】例えば、耐熱性繊維束として炭素繊維を用
いる場合は、炭素繊維にて管状支持体を作製し、多孔質
層の原料体（または溶液）を塗布したのち、酸化性雰囲
気下４００℃以下で一旦加熱硬化し、その後不活性雰囲
気中１０００℃以上で加熱して多孔質層を形成させる。For example, when carbon fibers are used as the heat-resistant fiber bundle, a tubular support is made of carbon fibers, and the raw material (or solution) for the porous layer is applied. , And then heat and cure at 1000 ° C. or more in an inert atmosphere to form a porous layer.
【００２８】また、耐熱性繊維束として耐炎化繊維を用
いる場合は、耐炎化繊維にて管状支持体を作製した後、
炭化処理し、多孔質層の原料体（または溶液）を塗布し
て酸化性雰囲気下４００℃以下で一旦加熱硬化し、その
後不活性雰囲気中１０００℃以上で加熱して多孔質層を
形成させる。When oxidized fiber is used as the heat-resistant fiber bundle, a tubular support is made of the oxidized fiber,
A carbonization treatment is performed, and a raw material (or solution) for the porous layer is applied, and is once heated and cured at 400 ° C. or lower in an oxidizing atmosphere, and then heated at 1000 ° C. or higher in an inert atmosphere to form a porous layer.
【００２９】なお、１回目の炭化を１０００℃以上で行
い、２回目の炭化を２０００℃以上で行うこともでき
る。The first carbonization may be performed at 1000 ° C. or more, and the second carbonization may be performed at 2000 ° C. or more.
【００３０】図２には、管状支持体の概要図（Ａ）と、
管状支持体表面の拡大図（Ｂ）とを例示した。管状支持
体が耐熱性繊維束４０の編織物よりなる構造体である場
合を示したが、編物の場合の編み方、織物の場合の織り
方、組み紐の組方等、編み方は特に制限されない。FIG. 2 shows a schematic view (A) of a tubular support,
An enlarged view (B) of the surface of the tubular support is illustrated. Although the case where the tubular support is a structure made of a knitted fabric of the heat-resistant fiber bundle 40 is shown, the knitting method is not particularly limited, such as a knitting method for a knitted material, a weaving method for a woven fabric, a braided braid, and the like. .
【００３１】管状支持体は、高圧下での強度、形態安定
性が機能として求められるため、耐熱性および機械的な
強度に大きく貢献するものであればよく、分離膜として
の機能を有する必要はない。このため、管状支持体を構
成する耐熱性繊維束には、形態および特性の温度依存性
が低いことが求められる。Since the tubular support is required to have high pressure strength and morphological stability as functions, it is sufficient that the support greatly contributes to heat resistance and mechanical strength. It is not necessary to have a function as a separation membrane. Absent. For this reason, the heat-resistant fiber bundle constituting the tubular support is required to have low temperature dependence of the form and characteristics.
【００３２】具体的には、耐熱性繊維束の２５℃に対す
る１００℃での形態の温度変化率は４％以下が好まし
く、２％以下がより好ましい。Specifically, the rate of temperature change of the heat-resistant fiber bundle at 100 ° C. with respect to 25 ° C. is preferably 4% or less, more preferably 2% or less.
【００３３】また、同様の観点から、耐熱性繊維束の２
５℃に対する８０℃での引張強さの温度変化率は、１０
％以下が好ましく、３％以下がより好ましい。From the same viewpoint, the heat-resistant fiber bundle 2
The temperature change rate of tensile strength at 80 ° C. to 5 ° C. is 10
% Or less, and more preferably 3% or less.
【００３４】更に、管状支持体には圧力損失が小さいこ
とが要求され、流体が濾過作用を受ける際、管状支持体
略円の半径方向に容易に移動できる程度の多孔度を有し
ていれば良く、繊維束を構成する単糸は流体中で束構造
を損なわない程度のものであれば良い。Further, the tubular support is required to have a small pressure loss. If the fluid has a porosity enough to easily move in a radial direction of a substantially circular shape of the tubular support when the fluid undergoes a filtering action. It is sufficient that the single yarn constituting the fiber bundle does not impair the bundle structure in the fluid.
【００３５】圧力損失を小さくするために、繊維束を構
成する単糸直径を小さくすることが有効であるが、単糸
直径が小さくなるにつれ編織物に加工する際の単糸切れ
が発生しやすくなる。In order to reduce the pressure loss, it is effective to reduce the diameter of the single yarn constituting the fiber bundle. However, as the diameter of the single yarn decreases, single yarn breakage tends to occur when processing into a knitted fabric. Become.
【００３６】以上の理由から、耐熱性繊維束を構成する
単糸の直径は４μｍ以上が好ましく、また、１０μｍ以
下が好ましく、８μｍ以下がより好ましい。For the above reasons, the diameter of the single yarn constituting the heat-resistant fiber bundle is preferably at least 4 μm, more preferably at most 10 μm, more preferably at most 8 μm.
【００３７】なお、単糸直径が４μｍ以上であれば、編
織物とする際の加工性に優れると言う利点もある。ま
た、１０μｍ以下であれば、同一仕様（管状支持体の外
周寸法、繊維束の数、繊維束を構成する単糸数が同一で
あること）の管状支持体で比較した場合、圧力損失が抑
制でき、十分な引張強度および良好な生産性を実現でき
る。If the diameter of the single yarn is 4 μm or more, there is also an advantage that the workability in forming a knitted fabric is excellent. Further, when the diameter is 10 μm or less, the pressure loss can be suppressed when compared with a tubular support having the same specification (the outer peripheral dimension of the tubular support, the number of fiber bundles, and the number of single yarns constituting the fiber bundle are the same). , Sufficient tensile strength and good productivity can be realized.
【００３８】耐熱性繊維束としては、管状支持体の耐熱
性の観点から、高温領域において溶出物質が少ないもの
であれば良く、低温から高温までの幅広い温度領域で溶
出物質がほとんどないポリアクリロニトリル系の耐炎化
繊維またはポリアクリロニトリル系の炭素繊維により構
成されたものが好ましい。From the viewpoint of the heat resistance of the tubular support, the heat-resistant fiber bundle may be any material as long as it has a small amount of eluted substances in a high-temperature region, and a polyacrylonitrile-based material having almost no eluted substances in a wide temperature range from low to high temperatures. It is preferable to use a fiber made of flame-resistant fiber or polyacrylonitrile-based carbon fiber.
【００３９】ポリアクリロニトリル系の耐炎化繊維とし
ては、少なくともアクリロニトリル９０モル％以上、好
ましくは９４モル％以上を含有する前駆体繊維束を、緊
張下、酸化性雰囲気下１８０℃以上で、耐炎化密度が
１．３０ｇ／ｃｍ3以上となるように熱処理したものが
好ましい。As the polyacrylonitrile-based flame-resistant fiber, a precursor fiber bundle containing at least 90 mol% or more, preferably 94 mol% or more of acrylonitrile, is subjected to a flame-resistant density of 180 ° C. or more under tension and in an oxidizing atmosphere. Is preferably 1.30 g / cm 3 or more.
【００４０】また、ポリアクリロニトリル系の炭素繊維
としては、上述の耐炎化繊維を不活性雰囲気中下３００
℃以上で、密度が１．７０ｇ／ｃｍ3以上、好ましくは
１．７６ｇ／ｃｍ3以上となるように数分間熱処理した
ものが好ましい。Further, as the polyacrylonitrile-based carbon fiber, the above-mentioned oxidized fiber may be used under an inert atmosphere for 300 minutes.
℃ above, density of 1.70 g / cm 3 or more, preferably is preferable that heat-treated for several minutes so that the 1.76 g / cm 3 or more.
【００４１】以上に説明した様に、本発明の高耐熱性多
孔質管状膜では、ポリアクリロニトリル系の耐炎化繊
維、ポリアクリロニトリル系の炭素繊維、ポリアクリロ
ニトリル系重合体の熱処理体、フェノール樹脂等の熱硬
化性樹脂の熱処理体等の耐熱材が好適に使用されるが、
これらの耐熱材を使用した場合、金属やセラミックの焼
結体を含む従来品と比較して、金属が溶出することはな
く、耐酸性に優れ、粒子が溶出することが無いなど、更
なる利点がある。As described above, in the highly heat-resistant porous tubular membrane of the present invention, the polyacrylonitrile-based oxidized fiber, the polyacrylonitrile-based carbon fiber, the heat-treated polyacrylonitrile-based polymer, the phenol resin, etc. A heat-resistant material such as a heat-treated body of a thermosetting resin is preferably used,
When these heat-resistant materials are used, compared to conventional products that include sintered bodies of metals and ceramics, there are further advantages such as no metal elution, excellent acid resistance, and no particle elution. There is.
【００４２】また、これらの耐熱材は機械的強度にも優
れるため、本発明の高耐熱性多孔質管状膜においては、
管状構造の破壊強度として０．７ＭＰａ以上の破裂強度
が実現できる。Further, since these heat-resistant materials are also excellent in mechanical strength, in the high heat-resistant porous tubular membrane of the present invention,
Burst strength of 0.7 MPa or more can be realized as the breaking strength of the tubular structure.
【００４３】[0043]
【実施例】以下、実施例により本発明を具体的に説明す
る。なお、以下の条件は、実施例において全て同一とし
た。また、特に明記しない限り、試薬等は市販の高純度
品を使用した。The present invention will be described below in detail with reference to examples. The following conditions were all the same in the examples. Unless otherwise specified, commercially available high-purity reagents were used.
【００４４】（ア）耐熱性繊維束前駆体の製造：アクリ
ロニトリル９５モル％を含有する、繊維束の構成単糸数
が１０００本、単糸テックスが０．１３ｔｅｘである重
合体繊維束を使用した。(A) Production of heat-resistant fiber bundle precursor: A polymer fiber bundle containing 95 mol% of acrylonitrile, the number of single yarns constituting the fiber bundle being 1,000, and the single yarn tex being 0.13 tex was used.
【００４５】（イ）耐熱性繊維束の製造：耐熱性繊維束
前駆体を２３０℃、０．８グラム／テックスの緊張下、
酸化性雰囲気下１時間で熱風処理した。その後、０．９
グラム／テックスの緊張下、不活性雰囲気下４００℃か
ら１６００℃まで均一な昇温勾配で２分間の炭化処理を
行い耐熱性繊維束を製造した。得られた炭素繊維の密度
は１．７７ｇ／ｃｍ3であった。(A) Production of heat-resistant fiber bundle: heat-resistant fiber bundle precursor was heated at 230 ° C. under a tension of 0.8 g / tex.
Hot air treatment was performed for 1 hour in an oxidizing atmosphere. Then 0.9
Under a tension of gram / tex, carbonization treatment was performed for 2 minutes from 400 ° C. to 1600 ° C. in an inert atmosphere under a uniform temperature gradient to produce a heat-resistant fiber bundle. The density of the obtained carbon fiber was 1.77 g / cm 3 .
【００４６】（ウ）管状支持体：耐熱性繊維束を３２本
用い、外径φ２ｍｍの管状支持体を製造した。(C) Tubular support: A tubular support having an outer diameter of 2 mm was manufactured using 32 heat-resistant fiber bundles.
【００４７】（エ）多孔質層：管状支持体の外面に、管
状支持体に対してフェノール樹脂（大日本インキ化学
（株）社製フェノライト５９００）を濃度が３６質量％
となるようエタノールを溶媒とするフェノール樹脂溶液
をコーティングし、酸化性雰囲気２６０℃で加熱硬化
後、再度炭化処理して多孔質層を形成した。(D) Porous layer: On the outer surface of the tubular support, a phenolic resin (Phenolite 5900 manufactured by Dainippon Ink and Chemicals, Inc.) was used at a concentration of 36% by mass relative to the tubular support.
After coating with a phenol resin solution using ethanol as a solvent and heating and curing at 260 ° C. in an oxidizing atmosphere, carbonization was performed again to form a porous layer.
【００４８】また、耐熱性繊維束の特性の温度依存性を
以下の手順で測定した。The temperature dependence of the properties of the heat-resistant fiber bundle was measured according to the following procedure.
【００４９】（ア）形態の温度変化率（％）は２５℃及
び１００℃において耐熱性繊維束のサンプル長をノギス
で測定し、以下の式により算出した； 形態の温度変化率（％）＝１００× ｛（２５℃での寸法）−（１００℃での寸法）｝ ／（２５℃での寸法）。(A) The temperature change rate (%) of the form was determined by measuring the sample length of the heat-resistant fiber bundle with a caliper at 25 ° C. and 100 ° C., and calculated by the following equation: Temperature change rate (%) of the form = 100 × {(dimension at 25 ° C.) − (Dimension at 100 ° C.)} / (Dimension at 25 ° C.)
【００５０】（イ）引張強さの温度変化率（％）は、２
５℃及び８０℃において耐熱性繊維束の引張強さをＪＩ
Ｓ Ｌ １０１３に準拠して測定し、以下の式により算
出した； 引張強さの温度変化率（％）＝１００× ｛（２５℃での引張強さ）−（８０℃での引張強さ）｝ ／（２５℃での引張強さ）。(A) The temperature change rate (%) of tensile strength is 2
The tensile strength of the heat-resistant fiber bundle at 5 ° C and 80 ° C was measured by JI
Measured in accordance with SL 1013 and calculated by the following equation: Temperature change rate (%) of tensile strength = 100 × ｛(tensile strength at 25 ° C.) − (Tensile strength at 80 ° C.) ｝ / (Tensile strength at 25 ° C.).
【００５１】更に、高耐熱性多孔質管状膜の特性を以下
の方法によって評価した。Further, the properties of the high heat-resistant porous tubular membrane were evaluated by the following methods.
【００５２】（ア）多孔質層における最大孔径：ＪＩＳ
Ｋ ３８３２に準拠し、ＰＯＲＯＵＳ ＭＡＴＥＲＩ
ＡＬＳ ＩＮＣ．社製Ｐｅｒｍ−Ｐｏｒｏｍｅｔｅｒに
より測定した。(A) Maximum pore size in the porous layer: JIS
In accordance with K 3832, POROUS MATERI
ALS INC. It was measured by Perm-Porometer manufactured by the company.
【００５３】（イ）破裂強度：内圧法により測定した。
即ち、高耐熱性多孔質管状膜の片端を閉じ、もう一方の
片端から蒸留水を導水した。そして、蒸留水を徐々に加
圧し、高耐熱性多孔質管状膜が破裂したときの蒸留水圧
力を計測した。加圧のステップは２４．５ｋＰａとし、
各圧力での保持時間は３０秒とした。(A) Burst strength: Measured by the internal pressure method.
That is, one end of the high heat-resistant porous tubular membrane was closed, and distilled water was introduced from the other end. Then, the distilled water was gradually pressurized, and the pressure of the distilled water when the highly heat-resistant porous tubular membrane burst was measured. The pressure step is 24.5 kPa,
The holding time at each pressure was 30 seconds.
【００５４】（ウ）濾過試験：試験液として、２６０
℃、０．１９６ＭＰａの加圧水を用いた以外は、ＪＩＳ
Ｋ ３８３１に準拠して測定した。(C) Filtration test: As a test solution, 260
JIS, except that pressurized water of 0.196 MPa was used.
It was measured in accordance with K3831.
【００５５】（エ）処理水の水質評価： 高耐熱性多孔
質管状膜０．２ｇを蒸留水２０ｇ中に８０℃で２４時間
浸漬処理し、処理後の水をＪＩＳ Ｋ ０１０２．２２
に準拠してＴＯＣを測定した。(D) Evaluation of water quality of treated water: 0.2 g of the highly heat-resistant porous tubular membrane was immersed in 20 g of distilled water at 80 ° C. for 24 hours, and the treated water was subjected to JIS K0102.22.
The TOC was measured according to.
【００５６】［実施例１］単糸直径が６μｍで、形態お
よび引張強さの温度変化率が、いずれも１％である耐熱
性繊維束を製造した。得られた耐熱性繊維束を組み紐状
として管状支持体を作製した。[Example 1] A heat-resistant fiber bundle having a single yarn diameter of 6 µm and a rate of temperature change of form and tensile strength of 1% was manufactured. The resulting heat-resistant fiber bundle was braided into a tubular support.
【００５７】その後、フェノール樹脂溶液をコーティン
グし、不活性雰囲気中２０００℃、１０分の条件で再度
炭化処理を行い、多孔質層を形成した。Thereafter, a phenol resin solution was coated and carbonized again at 2,000 ° C. for 10 minutes in an inert atmosphere to form a porous layer.
【００５８】得られた高耐熱性多孔質管状膜の多孔質層
における最大孔径は０．９μｍと十分小さく、破裂強度
は１．２７ＭＰａと十分高かった。また、濾過試験を行
った結果、座屈等の機械的ダメージは認められなかっ
た。更に、処理水の水質評価の結果、溶出物質等の存在
は認められず、良好な特性が確認された。The maximum pore size in the porous layer of the obtained high heat-resistant porous tubular membrane was sufficiently small at 0.9 μm, and the burst strength was sufficiently high at 1.27 MPa. As a result of a filtration test, no mechanical damage such as buckling was observed. Furthermore, as a result of the water quality evaluation of the treated water, the presence of eluted substances and the like was not recognized, and favorable characteristics were confirmed.
【００５９】［実施例２］多孔質層を形成する際の再炭
化処理の条件を２０００℃、１６分とする以外は、実施
例１と同様にして高耐熱性多孔質管状膜を製造した。Example 2 A high heat-resistant porous tubular film was produced in the same manner as in Example 1 except that the conditions of the recarburizing treatment for forming the porous layer were set to 2000 ° C. and 16 minutes.
【００６０】得られた高耐熱性多孔質管状膜の多孔質層
における最大孔径は１μｍと小さく、破裂強度は０．９
８ＭＰａと高く、濾過試験を行った結果、座屈等の機械
的ダメージは認められず、処理水の水質評価の結果、溶
出物質等の存在は認められなかった。The maximum pore size of the porous layer of the obtained high heat-resistant porous tubular membrane was as small as 1 μm, and the burst strength was 0.9.
As a result of performing a filtration test, mechanical damage such as buckling was not observed. As a result of water quality evaluation of the treated water, no eluting substance was found.
【００６１】［実施例３］耐熱性繊維束の単糸直径が１
３μｍである以外は、実施例１と同様にして高耐熱性多
孔質管状膜を製造した。Example 3 The heat-resistant fiber bundle had a single yarn diameter of 1
Except for 3 μm, a high heat-resistant porous tubular membrane was produced in the same manner as in Example 1.
【００６２】得られた高耐熱性多孔質管状膜は、濾過試
験において溶出物質は確認されず、破裂強度は０．３９
ＭＰａであった。The obtained heat-resistant porous tubular membrane did not show any eluting substances in a filtration test, and had a burst strength of 0.39.
MPa.
【００６３】［比較例１］市販のポリエチレン製膜（三
菱レイヨン社製ポリエチレン微多孔質中空糸膜；ＥＨＦ
膜）を用いて、管状膜を製造した。Comparative Example 1 A commercially available polyethylene membrane (polyethylene microporous hollow fiber membrane manufactured by Mitsubishi Rayon Co .; EHF)
Was used to produce a tubular membrane.
【００６４】１４０℃付近から略溶融状態となり、更に
高温では、使用に耐えるものではなかった。At about 140.degree. C., it was almost in a molten state. At a higher temperature, it was not usable.
【００６５】[0065]
【発明の効果】本発明によって、優れた耐熱性、耐腐食
性、耐圧性能、及び形態安定性を有し、かつ高強度で濾
過効率の高い高耐熱性多孔質管状膜を得ることが可能に
なる。According to the present invention, it is possible to obtain a high heat-resistant porous tubular membrane having excellent heat resistance, corrosion resistance, pressure resistance, form stability, high strength and high filtration efficiency. Become.
【００６６】本発明によって得られる高耐熱性多孔質管
状膜は、原子力発電および火力発電における復水の濾過
など主に高温、高圧下での分離膜として、また耐食プラ
ントにおける分離膜として有用に用いることができるな
ど、工業的な意義は極めて大きい。The highly heat-resistant porous tubular membrane obtained by the present invention is useful as a separation membrane mainly at high temperature and high pressure, such as filtration of condensate in nuclear power generation and thermal power generation, and as a separation membrane in a corrosion resistant plant. The industrial significance is extremely large.
【図１】本発明の高耐熱性多孔質管状膜の一例を説明す
るための模式的断面図である。FIG. 1 is a schematic cross-sectional view for explaining an example of a highly heat-resistant porous tubular membrane of the present invention.
【図２】本発明における管状支持体を説明するための模
式的斜視図（Ａ）と、表面の拡大図（Ｂ）である。FIG. 2 is a schematic perspective view (A) for explaining a tubular support in the present invention, and an enlarged view of the surface (B).
１０ 管状支持体 ２０ 多孔質層 ３０ 多孔質層 ４０ 耐熱性繊維束 Reference Signs List 10 tubular support 20 porous layer 30 porous layer 40 heat-resistant fiber bundle
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｄ０３Ｄ 15/00 Ｄ０３Ｄ 15/00 Ａ Ｄ０４Ｂ 1/14 Ｄ０４Ｂ 1/14 Ｄ０６Ｍ 15/41 Ｄ０６Ｍ 15/41 // Ｄ０６Ｍ 101:40 101:40 (72)発明者 吉田 晴彦 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央技術研究所内 (72)発明者 國澤 考彦 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央技術研究所内 Ｆターム(参考） 4D006 GA02 HA77 JA02A JA02B JA02C JA09A JA09B JA09C LA06 MA02 MA09 MA22 MB09 MB11 MB15 MB16 MC09 MC09X MC39 MC76 MC76X NA41 NA46 NA63 PA01 PB07 PC32 4L002 AA00 AA08 AB01 AB02 AC00 BB00 DA01 DA03 EA00 EA04 FA00 FA06 4L033 AA05 AA09 AB05 AB06 AC05 AC15 CA34 4L048 AA05 AA16 AB01 AB07 AC09 AC14 BA00 BA13 BB04 CA06 DA40 EB05 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) D03D 15/00 D03D 15/00 A D04B 1/14 D04B 1/14 D06M 15/41 D06M 15/41 // D06M 101: 40 101: 40 (72) Inventor Haruhiko Yoshida 20-1 Miyukicho, Otake City, Hiroshima Prefecture Inside Mitsubishi Rayon Co., Ltd. Central Research Laboratory (72) Inventor Norihiko Kunizawa 20-1 Miyukicho, Otake City, Hiroshima Prefecture No.F-term (reference) in Central Research Laboratory of Mitsubishi Rayon Co., Ltd. DA01 DA03 EA00 EA04 FA00 FA06 4L033 AA05 AA09 AB05 AB06 AC05 AC15 CA34 4L048 AA05 AA16 AB01 AB07 AC09 AC14 BA00 BA13 BB04 CA06 DA40 EB05
Claims (10)
管状支持体と、該管状支持体の内面および外面の少なく
とも一方に形成され、粒子状物質の分離機能を有する耐
熱性多孔質層とを含んでなることを特徴とする高耐熱性
多孔質管状膜。1. A tubular support mainly comprising a heat-resistant fiber bundle structure forming body, and a heat-resistant porous layer formed on at least one of an inner surface and an outer surface of the tubular support and having a function of separating particulate matter. A highly heat-resistant porous tubular membrane characterized by comprising:
らなることを特徴とする請求項１記載の高耐熱性多孔質
管状膜。2. The highly heat-resistant porous tubular membrane according to claim 1, wherein the tubular support is made of a knitted fabric of a heat-resistant fiber bundle.
での形態の温度変化率は４％以下であることを特徴とす
る請求項１又は２記載の高耐熱性多孔質管状膜。3. 100 ° C. for 25 ° C. of the heat-resistant fiber bundle
The highly heat-resistant porous tubular membrane according to claim 1 or 2, wherein the temperature change rate in the form (1) is 4% or less.
の引張強さの温度変化率は１０％以下であることを特徴
とする請求項１乃至３何れかに記載の高耐熱性多孔質管
状膜。4. The highly heat-resistant porous material according to claim 1, wherein a temperature change rate of the tensile strength at 80 ° C. with respect to 25 ° C. of the heat-resistant fiber bundle is 10% or less. Tubular membrane.
０μｍ以下であることを特徴とする請求項１乃至４何れ
かに記載の高耐熱性多孔質管状膜。5. The single yarn constituting the heat-resistant fiber bundle has a diameter of 1
The highly heat-resistant porous tubular membrane according to any one of claims 1 to 4, wherein the thickness is 0 µm or less.
系の耐炎化繊維またはポリアクリロニトリル系の炭素繊
維であることを特徴とする請求項１乃至５何れかに記載
の高耐熱性多孔質管状膜。6. The highly heat-resistant porous tubular membrane according to claim 1, wherein the heat-resistant fiber bundle is a polyacrylonitrile-based oxidized fiber or a polyacrylonitrile-based carbon fiber.
ことを特徴とする請求項１乃至６何れかに記載の高耐熱
性多孔質管状膜。7. The highly heat-resistant porous tubular membrane according to claim 1, wherein the maximum pore size of the porous layer is 3 μm or less.
合体の熱処理体または熱硬化性樹脂の熱処理体であるこ
とを特徴とする請求項１乃至７何れかに記載の高耐熱性
多孔質管状膜。8. The highly heat-resistant porous tubular membrane according to claim 1, wherein the porous layer is a heat-treated body of a polyacrylonitrile-based polymer or a heat-treated body of a thermosetting resin. .
を特徴とする請求項１乃至８何れかに記載の高耐熱性多
孔質管状膜。9. The highly heat-resistant porous tubular membrane according to claim 1, wherein the burst strength is 0.7 MPa or more.
支持体を製造する工程と、該管状支持体の内面および外
面の少なくとも一方に、多孔質層の原料体をコーティン
グする工程と、コーティングされた管状支持体を、所定
の温度で熱処理することにより多孔質層を形成する工程
とを含んでなることを特徴とする高耐熱性多孔質管状膜
の製造方法。10. A step of mainly producing a heat-resistant fiber bundle to form a tubular support, and a step of coating at least one of an inner surface and an outer surface of the tubular support with a raw material of a porous layer; Heat-treating the coated tubular support at a predetermined temperature to form a porous layer, thereby producing a highly heat-resistant porous tubular membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001118314A JP2002306936A (en) | 2001-04-17 | 2001-04-17 | High heat-resistant porous tubular membrane and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001118314A JP2002306936A (en) | 2001-04-17 | 2001-04-17 | High heat-resistant porous tubular membrane and method for manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002306936A true JP2002306936A (en) | 2002-10-22 |
Family
ID=18968725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001118314A Pending JP2002306936A (en) | 2001-04-17 | 2001-04-17 | High heat-resistant porous tubular membrane and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002306936A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007513755A (en) * | 2003-12-11 | 2007-05-31 | ポロメディア ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing tubular membrane |
| WO2016021731A1 (en) * | 2014-08-08 | 2016-02-11 | 東レ株式会社 | Solvent-resistant separation membrane |
-
2001
- 2001-04-17 JP JP2001118314A patent/JP2002306936A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007513755A (en) * | 2003-12-11 | 2007-05-31 | ポロメディア ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for producing tubular membrane |
| JP4718481B2 (en) * | 2003-12-11 | 2011-07-06 | イックス−フロウ ベスローテン フェンノートシャップ | Method for producing tubular membrane |
| WO2016021731A1 (en) * | 2014-08-08 | 2016-02-11 | 東レ株式会社 | Solvent-resistant separation membrane |
| JPWO2016021731A1 (en) * | 2014-08-08 | 2017-07-13 | 東レ株式会社 | Solvent-resistant separation membrane |
| US10099183B2 (en) | 2014-08-08 | 2018-10-16 | Toray Industries, Inc. | Solvent-resistant separation membrane |
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